Starch coated fibers having improved drying characteristics

ABSTRACT

A starch size composition for coating glass fibers at forming which has greatly improved drying properties. The composition includes a relatively narrow range of a noncrosslinked cationic starch and an underivatized starch that is preferably high in amylose and a portion of the granules of which are incompletely burst.

nIIn Rtaten Int Richard II. Ignatius Ailten, S.C.

Nov. 12, 11969 Oct. 26, 197 1 ()wens-Corning Iiberglas CorporationContinuation-impart of application Ser. No. 610,488, Ian. 20, 1967, nowabandoned.

Inventor Appl. No. Filed Patented Assignee STARCII COATED RIlBlERSIIAVING IMPROVED IIRYING CHARACTERISTICS 9 Claims, 1 Drawing Rig.

ILLS. CI 65/3, 117/126 00, 106/210, 106/213, 1 17/46 CA, 1 17/66 Int. Cl..C03c 25/02, C08b 25/02 lIield 011 Search 1 17/126 00, 46 CA, 66;106/210, 213; 260/2333, 233.5; 65/3 [56] References Cited UNITED STATESPATENTS 2,946,705 7/1960 Olsen 117/126 GQ 3,077,469 2/1963 Aszalos260/2333 3,167,468 1/1965 Lovelace et a1. 117/126 GQ 3,227,192 1/1966Griffiths 117/126 GO 3,320,080 5/1967 Mazzarella et al 106/213 PrimaryExaminerWilliam D. Martin Assistant Examiner-D. Cohen Attorneys-Staelinand Overman and William P, Hickey ABSTRACT: A starch size compositionfor coating glass fibers at forming which has greatly improved dryingproperties. The composition includes a relatively narrow range of anoncrosslinked cationic starch and an underivatized starch that ispreferably high in amylose and a portion of the granules of which areincompletely burst.

STARCII COATED FIBERS HAVING IMPROVED DRYING ClIIARACTlERlISTlICfi CROSSREFERENCE TO RELATED APPLICATIONS The present application is aContinuation-In-Part of my copending application Ser. No. 610,488, filedJan. 20, 1967 and now abandoned.

BACKGROUND OF THE INVENTION The present invention relates to starchlubricants for fibers; and more particularly to starch lubricants thatare applied to glass fibers at forming to protect them from abrasionthrough subsequent gathering, twisting, quilling, beaming and weavingoperations.

Starch lubricants of the type referred to are applied to glass fibersimmediately after attenuation and before being drawn together into astrand. Thereafter the strand is wound at high speed into a coiledpackage about a tubular form and this package is allowed to dry beforethe fibers are uncoiled and used in the subsequent twisting, beaming,quilling and weaving operations. During the drying of the coiledpackage, water migrates from the center of the package to its exposedsurfaces; and during this migration, a certain amount of coatingmaterials, particularly starch and cationic lubricants, are carried withthe water to produce a higher concentration of these materials at theexposed surface of the package than remain at the center of the package.

Solubilized amylose produces a gelable material which can be made to gelbefore being wound into the package, and this material has certaindesirable properties, one of which is that it is fast drying. Amylose isthe linear fraction of starch which is found in nature. Amylose issolubilized by solvating the primary and secondary OH groups in thestarch molecule. Upon being cooled, some hydrogen bonding takes placethrough a plurality of water molecules which connect the OH groups toproduce a gel. It is a property of amylose that a driving force existsduring drying to throw off some of these water molecules of the geluntil only one, or perhaps two, water molecules remain in the bondbetween the OH groups of adjoining molecular chains.

It has been known heretofore to incorporate cationic lubricants andnonionic lubricants into starch materials, including high amylose starchmaterials, in order to supplement the lubricating effect of the starch,particularly during the forming operation. The cationic lubricants arevery soluble in water and these lubricants appear to migrate to a greatextent with the water. Cationic lubricants, therefore while capable ofhydrogen bonding with the starch are thrown off to a large extent duringgelling and drying to become largely separated from the starch andthereby produce lubricating effects attributable to the materialsthemselves, rather than to a modification of the starch.

According to the present invention, it has been discovered that arelatively narrow range of noncrosslinked cationic starch containingammonium and phosphonium radicals can be incorporated with a gellingnonderivatized high amylose starch to give better drying properties,while also giving as good migration resistance as the underivatizedstarch. The prior art has not taught that such modification is possible.

According to the invention, a natural occurring starch fraction,preferably high in amylose, is modified so that the starch molecule ismade cationic, and this material is mixed with other naturally occurringstarch materials. It has been found that naturally occurring starchmaterials can be made cationic by attaching a nitrogen or phosphorusatom having an unshared pair of electrons thereon to the starchmolecule. Thereafter, a Bronstead-Lowry acid or a Lewis acid is reactedtherewith to produce a cationic starch molecule. It will be understoodthat the material attached to the original unshared pair of electrons,need not be a proton but can be any group having a positive unbalance.

It has been found that such cationic starch materials when added toother starch materials do not become separated from the starch materialsas do cationic lubricants. It appears that the cationic starch moleculesbecome hydrogen bonded to naturally occurring starch molecules duringgel formation through a multiplicity of water molecules, and that theydry to a stable form wherein they are bonded to another starch moleculethrough no more than one or two water molecules. The cationic starchmaterials therefore throw off water in substantially the same manner asthe naturally occuring starch materials, and are in themselvescompatible with the naturally occurring starch materials; so that thereis very little force tending to withdraw the cationic starch from awater chain upon drying. The cationic starch material, therefore,remains in place to decrease hydrogen bonding between the chains ofnaturally occurring starch material, to not only modify the gellingcharacteristics of the mixture and speed up drying, but to permanentlymodify the characteristics of the dried film.

An object of the present invention is the provision of a new andimproved starch lubricant which is fast drying and which does notproduce streaks in woven fabrics during burn-off.

A more particular object of the present invention is the provision of anew and improved starch material which will gel, but whose tendency toform g1obules in fiber coating apparatus is greatly reduced, and whichwill dry more quickly than the prior art high amylose materials.

Further objects and advantages of the present invention will becomeapparent to those skilled in the art to which the inven tion relatesfrom the following description of several preferred compositions whichembody the invention, as well as the accompanying teaching of theprinciples by which the improved properties are achieved.

BRIEF DESCRIPTION OF THE DRAWING The sole figure of the drawing is agraph of the percent of moisture that is lost at various drying timesfrom coiled packages of glass fibers, the fibers of which are sized withvarious starch based coating materials.

DESCRIPTION OF THE PREFERRED EMBODIMENTS It has been found that such amixture of a noncrosslinked cationic starch and a naturally occurringstarch of the gelling type, will form a modified type of gel that issofter and does not separate into globules during its application to thefibers. It has further been found that when the cationic starchderivative constitutes no more than approximately one third of thesolubilized material, the mixture will throw off water faster than doesthe unmodified starch material when forming a gel by itself withoutimpairing the migration and other properties of the composite film.

It will be apparent that while the cationic starch material can bondwith amylopectin in the same manner as it does with amylose to modifythe amylopectin characteristics, the modification of the amylose and itsgel forming characteristics has particular advantages making this classof materials the preferred materials.

It has been found that when a noncrosslinked cationic starch materialcomprises as low as 4 percent of the gelled and/or solubilized starchmaterial, a noticeable reduction in the number of streaks occurs in thefinished woven fabrics. This streak reduction is evident at allpercentage ranges up through those wherein the cationic starchderivative comprises 50 percent of the total gelled and/or solubilizedstarch. In some instances, it is desirable to incorporate incompletelyburst starch granules dispersed throughout the gelled and/or solubilizedstarch; and when such materials are used, it has been found that theamount of starch rub-off during subsequent twisting and quillingoperations is noticeably reduced up through concentrations wherein thecationic starch deriva tive comprises more than 33 percent of the gelledand/or solubilized starch. A mixture having improved overall propertiesis provided when the cationic starch derivative comprises fromapproximately 4 percent to approximately 33 percent by weight of thegelled and/or solubilized starch of the mixture.

The more preferred compositions appear to be formed when the cationicstarch derivative comprises from between approximately 4 percent to 15percent of the total gelled and/or solubilized starch.

EXAMPLE l A preferred starch lubricant material has the followingcomposition in percentage by weight:

High Amylore Starch 3.82% (50-60% amyloseS-40% amylopectin) CationicStarch 0.42 Nonionic Lubricant l.27% (hydrogenated vegetable oil)Emulsifier (polyoxyethylene 0.13% sorbitan monooleate) Other emulsifier(polyethylene 0. l 3% glycol) Wetting agent (alkylphenoxypoly 0.03%(ethyleneoxy) ethanol) Cationic Lubricant (tetraethylene 0.21% pentaminedistearate) Fungicide (tributyl tin oxide) ppm. Water Balance A starchhaving one b-dicthyl amine ethyl chloride hydrochloride group perglucose unit.

A mixture of solubilized and unsolubilized materials is formed bypassing a water suspension of a mixture of the natural occurring starchand the cationic starch through a jet cooker whose exit temperature iscontrolled to a temperature of2l0 F.; ;2 F.

Saturated steam at approximately 100 p.s.i. is throttled to the jetcooker to provide this exit temperature, and this exit temperatureprovides a degree of partial cook which corresponds to that produced bythe same materials when heated together in a pressure vessel at 254 F.The cationic lubricant and the polyethylene glycol are thoroughly mixedand heated to a temperature of approximately l70 F. and in approximately1/20 of the total volume of water that is used, and this mixture isallowed to cool to 120 F. before being added to the starch cooked asabove described. The vegetable oil, wetting agent and polyoxyethylenesorbitan monooleate are heated to l60 F. and U of the total volume ofwater is added to form an emulsion. This emulsion is blended into theabove described mixture and the tributyl tin oxide is added. The balanceof the water is blended into the mixture and the temperature of themixture is reduced to between 140 to 150' F. for application to glassfibers immediately after attenuation and prior to being coiled into apackage by a conventional padder or applicator.

Coiled packages of fibers produced as above described have the dryingcharacteristics designated as example i in table 1 below. Table lcompares the drying characteristics of the material of example l withthose of packages of fibers prepared in an identical manner but havingdifferent ratios of the cationic starch material and the naturallyoccurring starch.

material.

Table II gives a comparison of still other properties of the samematerials indicated in Table l. The following is alistingof the meaningof the properties listed in Table II: Ringer-indicates the percent offorming packages in which broken filaments gather into a ring as thestrands are drawn off of the forming packages. Rub-off-is the amount ofstarch material in unit weight/unit time that is lost in the form ofpowder when the coated strands are pulled over a contact point.Fly-indicates the unit weight/unit time of short broken filaments whichare lost when the coated strand is pulled over acontact point. Migrationindex-indicates the ratio of the weight of coating on the fibers on theoutside of the package divided by the weight of coating on the fibers atthe center of the package. Streaksgrading system from 0.0-4.0 resultingfrom visual: observation of streaks on partially heat cleaned yarnand/or fabric. Absence of streaks being graded 0.0.

Examples 2, 3 and 4 of Table I above give the corresponding results formixtures prepared in the same manner as Example 1, but differing only inthe percent of the unmodified starchand of the cationic starch. Thepercentage of these materials for each example is give nin the table. 7

As indicated above, the mixtures of materials in water that was appliedto the fibers in the above tests comprise approximately 5 percent withthe balance being water. The high amylose material containing 50 topercent amylose, 40 to 50 percent amylopectin when cooked at thetemperatures indicated above provides approximately percent ofincompletely burst starch granules some of which are partially broken togive soft husks and the balance of which are swollen but unburst. it isassumed that the starch from the burst granules which went into solutiondid so with the same amylose to amylopectin ratio as occurred in theunburst starch granules, so that the composition of the mixturecomprised: approximately 0.95 percent completely burst starch granules,2.85 percent incompletely burst starch granules, and 0.52 percent of thecationic starch. In the above compositions, therefore, the incompletelyburst starch granules comprises approximately 2.0 parts per part ofsolubilized starch, and the cationic starch comprised approximately0.306 part per part of solubilized starch. It will be apparent that theincompletely burst starch granules do not produce migration or streaks,and that the incompletely burst starch granules add their physicalproperties to the mixture. These effects become important in theoperations after forming as well as controlling migration duringforming, and the incompletely burst starch granules should preferably bepresent in an amount of approximately 1.0 to 20.0 parts per part of thesolubilized naturally occurring starch. 7

TABLE I [Forming tube drying rate (percent total moisture lost in Xhours)] Unmodifind Cationic Hours after forming starch, starch, Examplespercent percent 4 8 12 16 20 24 TABLE II Unmodified CationicMigrastarch, starch tion Examples percent percent Ringers Rub ofi FlyStatic Streaks index 100 0 46 66. 6X10-4 7. 8Xl0-4 2. 6 2.0 1.48 00 1046 49. 6X10-4 6. 5X10-4 l. 8 1.8 1. 56 15 29 48. 9X10-4 l0. 3X10-4 l.6 1. 8 1. 57 80 20 38 36. 8X10-4 7. 9X10-4 -1. 7 1. 5 1.44

The amount of the coating material which is applied to the fibers will,of course, effect the thickness of the coating which is applied to thefibers before drying as well as the amount which is left on the fibersafter drying. The percent of solids being drawn into a strand. Thestrand was then coiled into a package which was placed in a room havinga relative humidity of 50 percent for drying, and the package wasweighed after 3, 7, 19, 27, 46, 53 and 91 hours. The loss in weight thenwhich is used in the water mixture as well as the type of starch plottedto give the curve of the drawing, and is tabulated in used controls theviscosity of the water mixture. In those int l V- stances where thestarch material is principally amylopectin, a higher amount of naturallyoccurring starch solids can be EXAMPLE 8 used, and w1th high amylopectinstarches the material which 10 A f r i i was made according toexample 1. f the forms h completely Starch solution can range fGriffiths Pat. No. 3,227,192 using the following materials inapproximately 5 to approx1mately 12 percent by welght. parts b i h Wherehigh amylose materials i.e. those containing more than approximately 40percent amylose are used to form the gel, it Ingredients Amount isnecessary in most instances to limit the amount of starch 15 which isgelled to between approximately 2 percent and 6 per- Amykm Special 55(55% amylose) cent by we1ght of the water mixture. National HFS (cornstarch cross-linked 300 with phosphorus oxychloride and EXAMPLE 5 having27 percent by weight amyloae) Pureco Oil (hydrogenated cottonseed oil)135 A forming size was prepared in the same manner given in Tween 81(ethylene Oxide derivative 30 of a sorbitol ester) example 1 ttlisl1lngthe same proportions exceptmg that a ca Canon x (alkylimidazolinereacflon 60 home stare avmg a single2-chloroethyltrrbutylphosphonrproducmfmraethylene pcmamine um chloridegroup per glucose unit, was substituted for the caand stearic acid)tionic starch of example 1. The phosphonium material gave Carbwax 33ltmlyflhylene llfywlhavintl 72 substantially the same improvement inproperties as did the f' we'ghmfappmx'mmly gepal CA-630 (octyl phenoxypoly- 0.04 31111110111111 11 type cat1on1c starch of example 1.(mhyleneoxy) mm) The ab1l1ty of most materials to burn is decreased whenWater to giveasolids content of6% by weight nitrogen and/or phosphorusatoms are attached to the compounds. In the present instance, however,the rate of burn-off 30 is increased when the ammonium and phosphoniumgroups A size was prepared by mixing the .Amylon Special 55 starch areattached to the starch molecule. and the National l-lFS starch inapproximately one half of the total water, and cooking this slurry at198 to 209 F. in a jet EXAMPLE 6 cooker for a sufficient period of timeto thoroughly incor- A 5 percent solution of the cationic starch ofexample 1 was 35 pol'ate the Starch f the aqueous System Thereafter F qmade by dissolving in water at a temperature of approximately bowax hCanon the Twe en and an 190 F. This material was coated on previouslyweighed glass the Pureco were added and "f' thoroughly slides andallowed to dry over night at a temperature of 140 was PP glass i rsusing the procedure of exam- F. Four coated glass slides were thenweighed and placed in an Ple 7 and dnefi also accQrdmg to the ProcedureElven m f oven containing air heated to 600 F. One slide was removed 4Ple The molsture loss Show" by curve 20 oflhe drawmg' after an exposureof 5 minutes, another at 10 minutes, another EXAMPLE 9 at 15 minutes andanother at 20 minutes. A black deposit existed on each of the slides,and the slides were weighed again. The procedure of example 8 repeatedexcepting that the The percent of the coating which was burned off wascom size composition was prepared using 454 parts of Amylon Speputed andthese results are given in table Ill under example 6. tr 5 arch to 60parts of the National HFS starch. The dry- The same process was repeatedexcepting that the material of ing curve for this size is given by thecurve designated 30 in the example 5 was substituted for the material ofexample 1. The gpercent of burn-off is also given in table 111 for thiscationic Starch TABLE IV The process was also repeated using theunmodified starch [Percent mmsme lost time indicated] of examples 1, 2and 3, and the rate of burn-off of the un- Hours at room temperature2111-5. s.. A M modlfied starch 1s g1ven in table III. Curve 1 3 7 m 2746 53 m R TABLE III 10 .00 1.14 2.16 3. 62 4 .10 5. 44 s. 73 6. 7a 0.0055 20..- .60 1.01 1.70 2.70 3 44 4.3. 4.40 5.41: 8.98 30.- .68 1.00 2.00.121 as; 4.31 5.01 0.11 0.23

Percent Burn-off At 600 F.

It has been found that part1ally burst or swollen but unburst granulesof a high amylose starch have gelling properties even 75 though they arenot completely dispersed or solubilized. It has m i further been foundthat these unburst granules are bigger than Nam"! cammc Demamed thespace between the fibers of a strand and, therefore, cannot Starch ofStarch of Starch of Normal Corn I h l h f d h f h Minutes Example 4Example 1 Example 5 starch migrate. t as a so een oun t at aconcentration 0 e ca- 6 5 Home starch about these unburst granules aidsin the removal s 5Z6 6L8 692 of water from the granules so that a higherpercentage of ca- 10 63,4 743 743 home starch in the solublllzed starcharound the granules 1s 15 68-7 71.5 83.0 0 desirable than would beacceptable if the gel did not include 782 unburst granules. There is,therefore, an averaging effect, and 70 it appears that improved dryingproperties are achieved when the cationic starch is present in an amountof from approxi- EXAMPLE7 mately 4 to approximately 15 percent (mostpreferably 10 percent) of the gelled starch material, whether it 1scompletely The forming size of example 1 was applied to 408 glass burstor not. Improved overall properties are achieved when a fibers having adiameter of 0.00035 inch at forming prior to high percentage of the highamylose starch is present as unburst starch granules. The preferredmaterials, therefore, will comprise unburst starch granules in an amountof from approximately 50 to approximately 90 percent of the total starchmaterial, desirably from approximately 60 percent to approximately 80percent, and most desirably approximately 67 percent. Sixty-sevenpercent unburst starch granules is achieved when a starch compositioncomprising 90 percent high amylose and 10 percent cationic starch iscooked to burst approximately 25 percent of the high amylose granules. Acomplete size formulation will also include an emulsion of a nonioniclubricant of from approximately percent to approximately 50 percent ofthe total starch material (preferably from to 30 percent), and acationic lubricant of up to approximately 10 percent (preferably 2percent to 5 percent) of the total starch material.

Preferred size formulations, therefore, will comprise the followingingredients in approximate percentages by weight:

It will be apparent that the objects heretofore enumerated as well asothers have been accomplished, and that there has been provided a newand improved starch containing lubricant for fibers which will dryquickly when on fibers in a coiled package to produce low streak levelsin finished fabrics and to further produce certain desirable gellingcharacteristics when incorporated in high amylose starch solutions.

While the invention has been described in considerable detail, I do notwish to be limited to the particular compositions described in detail;and it is my intention to cover hereby all novel adaptations of theprinciples disclosed, as well as modifications of these principles whichwill come within the practice of those skilled in the art to which theinvention relates, and which are covered by the appended claims.

lclaim:

1. In the method of forming glass fibers comprising the steps of:drawing glass filaments from a molten supply of glass at a high rate ofspeed; gathering the filaments and combining them into a strand;applying a fast drying sizing composition having unburst starch granulesto the filaments as they are being drawn, said size consistingessentially of an aqueous material having from approximately 2 toapproximately 12 percent by weight of a gelling starch material windingthe sized strand on a rapidly rotating forming tube; and conditioningthe strand on the forming tube to reduce the moisture content to anamount which is acceptable for twisting the strand into yarn; theimprovement which comprises: employing as the size a compositioncomprising: an incompletely burst starch granule portion of fromapproximately 50 percent to approximately 90 percent of the totalstarch, and a cationic starch portion from the group consisting ofnoncrosslinked Nitrogen and Phosphorus starch ethers and esters of fromapproximately v4 percent-to approximately 15 percent by weight of thetotal starch.

2. The method. of claim 1 wherein the starch material comprises from2too percent by weight of the size of a starch having an amylose toamylopectin ratio of more than 40 percent by weight.

3. The method of claim 1 wherein the cationic-starch is made cationic byan ammonium radical.

4. The method of claim 1 wherein the cationic starch is made cationic bya phosphonium radical.

, 5. 1n the method of forming glass fibers which comprises the steps of:drawing glass filaments from a molten supply of glass at a high rate ofspeed; gathering the filaments and combining them into a strand;applying a fast drying sizing composition having unburst starch granulesto the filaments as they are being drawn, said size consistingessentially of an aqueous material having from 2 to 12 percent by weightof a starch mixture; winding the sized strand on a rapidly rotatingforming tube; and conditioning the strand on the forming tube to reducethe moisture content to an amount which is acceptable for twisting thestrand into yarn; the improvement which comprises employing as the sizea composition comprising: an incompletely burst starch granule portionof from approximately 60 percent to approximately percent of the totalstarch, and a cationic starch portion from the group consisting ofnoncrosslinked Nitrogen and Phosphorus starch ethers and esters of fromapproximately 4 percent to approximately 15 percent by weight of thetotal starch; 5 to 50 percent by weight of a nonionic lubricant basedupon the weight of starch mixture, and up to 10 percent by weight of acationic lubricant based upon the weight of starch mixture.

6. In the method of forming a glass fiber fabric which comprises thesteps of: drawing glass filaments from a molten supply of glass at ahigh rate of speed; gathering the filaments and combining them into astrand; applying an aqueous sizing composition to the filaments as theyare being drawn; winding the sized strand on a rapidly rotating formingtube; conditioning the strand wound on the forming tube to reduce themoisture content of the sizing composition to an amount which isacceptable for twisting the strand into yarn; weaving the yarn into acloth; heating the cloth to remove the sizing composition and set thefibers; the improvement which comprises: applying a fast drying aqueouscomposition consisting essentially of: from 2 to 12 percent by weight ofa starch mixture having an incompletely burst starch granule portion offrom approximately 50 percent to approximately percent of the totalstarch, and a cationic starch portion from the group consisting ofnoncrosslinked Nitrogen and Phosphorus starch ethers and esters of fromapproximately 4 percent to approximately 15 percent by weight of thetotal starch; 5 to 50 percent by weight of a nonionic lubricant basedupon the weight of starch mixture; and up to 10 percent by weight of acationic lubricant based upon the weight of starch mixture.

7. A sized woven glass fabric comprising glass fibers sized with a fastdrying, aqueous size composition which is readily removed bysubsequently heating the sized woven fabric at a temperature effectingthermo destruction of the sizing composition and volatilizing theorganic components thereof, said sizing composition prior to heatingconsisting essentially of the dry residue of an aqueous compositionconsisting essentially of: from 2 to 12 percent by weight of a starchmixture having an incompletely burst starch granule portion of fromapproximately 60 percent to approximately 80 percent of the totalstarch, and a cationic starch portion from the group consisting ofnoncrosslinked Nitrogen and Phosphorus starch ethers and esters of fromapproximately 4 percent to approximately 15 percent by weight of thetotal starch; 5 to 50 percent by weight of a nonionic lubricant basedupon the weight of starch mixture; and up to 10 percent by weight basedupon the weight of starch mixture of a cationic lubricant.

8. In the method of forming glass fibers which comprises the steps of:drawing glass filaments from a molten supply of glass at a high rate ofspeed; gathering the filaments and combining them into a strand;applying a fast drying size composition to the fibers as they are beingdrawn; winding the sized strand on a rapidly rotating forming tube; andconditioning the strand in the forming tube to reduce the moisturecontent to an amount which is acceptable for twisting the strand into ayarn; the improvement which comprises: employing as the size acomposition consisting essentially of the following in approximatepercentages lncompletely burst granules Cationic lubricant Water 0.005to 1.0% Balance.

llll

tion consisting essentially of the following in approximate percentagesby weight incompletely burst granules of high amylose starch 3'82Cationic starch 0.42 Nonionic lubricant 1.27

emulsifier 0 26 Wetting agent 0.03 Cationic lubricant 0.2l WaterBalance.

2. The method of claim 1 wherein the starch material comprises from 2 to6 percent by weight of the size of a starch having an amylose toamylopectin ratio of more than 40 percent by weight.
 3. The method ofclaim 1 wherein the cationic starch is made cationic by an ammoniumradical.
 4. The method of claim 1 wherein the cationic starch is madecationic by a phosphonium radical.
 5. In the method of forming glassfibers which comprises the steps of: drawing glass filaments from amolten supply of glass at a high rate of speed; gathering the filamentsand combining them into a strand; applying a fast drying sizingcomposition having unburst starch granules to the filaments as they arebeing drawn, said size consisting essentially of an aqueous materialhaving from 2 to 12 percent by weight of a starch mixture; winding thesized strand on a rapidly rotating forming tube; and conditioning thestrand on the forming tube to reduce the moisture content to an amountwhich is acceptable for twisting the strand into yarn; the improvementwhich comprises employing as the size a composition comprising: anincompletely burst starch granule portion of from approximately 60percent to approximately 80 percent of the total starch, and a cationicstarch portion from the group consisting of noncrosslinked Nitrogen andPhosphorus starch ethers and esters of from approximately 4 percent toapproximately 15 percent by weight of the total starch; 5 to 50 percentby weight of a nonionic lubricant based upon the weight of starchmixture, and up to 10 percent by weight of a cationic lubricant basedupon the weight of starch mixture.
 6. In the method of forming a glassfiber fabric which comprises the steps of: drawing glass filaments froma molten supply of glass at a high rate of speed; gathering thefilaments and combining them into a strand; applying an aqueous sizingcomposition to the filaments as they are being drawn; winding the sizedstrand on a rapidly rotating forming tube; conditioning the strand woundon the forming tube to reduce the moisture contEnt of the sizingcomposition to an amount which is acceptable for twisting the strandinto yarn; weaving the yarn into a cloth; heating the cloth to removethe sizing composition and set the fibers; the improvement whichcomprises: applying a fast drying aqueous composition consistingessentially of: from 2 to 12 percent by weight of a starch mixturehaving an incompletely burst starch granule portion of fromapproximately 50 percent to approximately 90 percent of the totalstarch, and a cationic starch portion from the group consisting ofnoncrosslinked Nitrogen and Phosphorus starch ethers and esters of fromapproximately 4 percent to approximately 15 percent by weight of thetotal starch; 5 to 50 percent by weight of a nonionic lubricant basedupon the weight of starch mixture; and up to 10 percent by weight of acationic lubricant based upon the weight of starch mixture.
 7. A sizedwoven glass fabric comprising glass fibers sized with a fast drying,aqueous size composition which is readily removed by subsequentlyheating the sized woven fabric at a temperature effecting thermodestruction of the sizing composition and volatilizing the organiccomponents thereof, said sizing composition prior to heating consistingessentially of the dry residue of an aqueous composition consistingessentially of: from 2 to 12 percent by weight of a starch mixturehaving an incompletely burst starch granule portion of fromapproximately 60 percent to approximately 80 percent of the totalstarch, and a cationic starch portion from the group consisting ofnoncrosslinked Nitrogen and Phosphorus starch ethers and esters of fromapproximately 4 percent to approximately 15 percent by weight of thetotal starch; 5 to 50 percent by weight of a nonionic lubricant basedupon the weight of starch mixture; and up to 10 percent by weight basedupon the weight of starch mixture of a cationic lubricant.
 8. In themethod of forming glass fibers which comprises the steps of: drawingglass filaments from a molten supply of glass at a high rate of speed;gathering the filaments and combining them into a strand; applying afast drying size composition to the fibers as they are being drawn;winding the sized strand on a rapidly rotating forming tube; andconditioning the strand in the forming tube to reduce the moisturecontent to an amount which is acceptable for twisting the strand into ayarn; the improvement which comprises: employing as the size acomposition consisting essentially of the following in approximatepercentages Incompletely burst granules of high amylose starch 2 to 6%Cationic Starch 0.2 to 1.0% Nonionic lubricant 0.10 to 3.0% Emulsifier0.020 to 0.50% Wetting agent 0.0 to 0.26% Cationic lubricant 0.005 to1.0% Water Balance.
 9. In the method of forming glass fibers whichcomprises the steps of: drawing glass filaments from a molten supply ofglass at a high rate of speed; gathering the filaments and combiningthem into a strand; applying a fast drying size composition to thefibers as they are being drawn winding the sized strand on a rapidlyrotating forming tube; and conditioning the strand in the forming tubeto reduce the moisture content to an amount which is acceptable fortwisting the strand into a yarn; the improvement which comprises:employing as the size a composition consisting essentially of thefollowing in approximate percentages by weight Incompletely burstgranules of high amylose starch 3.82 Cationic starch 0.42 Nonioniclubricant 1.27 emulsifier 0.26 Wetting agent 0.03 Cationic lubricant0.21 Water Balance.